Cleaning agent for semiconductor provided with metal wiring

ABSTRACT

A cleaning agent for a microelectronic device provided with metal wiring, which has an excellent ability to remove polishing particle residues derived from a polishing agent and an excellent ability to remove metallic residues on an insulating film, and has excellent anticorrosiveness to the metal wiring. The cleaning agent is used at a step subsequent to chemical mechanical polishing in a manufacturing process of a microelectronic device in which a metal wiring, e.g., copper or tungsten, is formed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the priority of Japanese Patent Application No.2010-017772 filed on 29 Jan. 2010 and entitled “Cleaning Agent forSemiconductor Provided with Tungsten Wiring” Japanese Patent ApplicationNo. 2010-072824 filed on 26 Mar. 2010 and entitled “Cleaning Agent forSemiconductor Provided with Copper Wiring,” both of which are herebyincorporated herein by reference in their entireties.

FIELD

The present invention relates to a cleaning agent used for cleaning asurface subsequent to chemical mechanical polishing (CMP) in amanufacturing process of a microelectronic device, and particularlyrelates to a post-CMP cleaning agent for a microelectronic deviceprovided with metal wiring (e.g., tungsten or a tungsten alloy, copperor a copper alloy) on the surface thereof.

BACKGROUND

Market needs such as high performance and miniaturization has resultedin the need for more integrated semiconductor elements onmicroelectronic devices. For example, a high-level planarizationtechnique for forming a finer circuit pattern is necessary, wherein aCMP step of polishing a wafer surface using a polishing slurry(hereinafter, abbreviated to a CMP slurry) containing particulates ofalumina or silica is effectuated.

In this CMP step, however, various substances remain on the device afterpolishing, for example: polishing particulates such as alumina andsilica in the CMP slurry (hereinafter, abrasive grains), iron nitrateaqueous solutions added to accelerate polishing, anticorrosive added tosuppress corrosion of a metal, and residues of a polished metal wiringand zinc and magnesium metals used on a side of said metal wiring. Theseresidues can have an adverse effect on electrical properties of thesemiconductor such as shorting. Accordingly, it is necessary to removethese residues prior to proceeding to the next manufacturing step.

In the related art for tungsten CMP, post-CMP methods typically use anammonia and hydrogen peroxide aqueous solution or a hydrochloric acidand hydrogen peroxide aqueous solution in combination with a dilutedhydrofluoric acid aqueous solution. In such a method, however, thewiring metal can be substantially corroded. Accordingly, the methodcannot be applied to modern microelectronic devices having finepatterns. In order to avoid this corrosion, a cleaning process using acleaning agent containing an organic acid that is less corrosive totungsten, such as citric acid and oxalic acid, and a chelating agentsuch as amino polycarboxylic acid has been proposed (Japanese PatentApplication Laid-Open No. 10-72594).

In the related art for copper CMP, post-CMP methods typically use acidiccleaning agents containing an organic acid such as citric acid andoxalic acid as a principal component (Japanese Patent ApplicationLaid-Open No. 2001-7071). However, while these cleaning agents have anexcellent ability to remove metallic residues, the cleaning agents arehighly corrosive to the copper wiring. In order to improve thiscorrosiveness, alkaline cleaning agents containing an alkanolamine as aprincipal component are known (Japanese Patent Application Laid-Open No.11-74243). These cleaning agents have low corrosivity to the copperwiring and have an excellent ability to remove organic residues derivedfrom the anticorrosive added in the CMP slurry. That said, thesecleaning agents have a poor ability to remove metallic residues.Alternatively, alkaline cleaning agents having an ability to removemetallic residues are known, said cleaning agents including an organicacid, such as succinic acid and oxalic acid, and an alkanolamine as theprincipal component (Japanese Unexamined Patent Application PublicationNo. 2003-536258). However, while these cleaning agents have an excellentability to remove metallic and organic residues, the cleaning agents arehighly corrosive to the copper wiring. Accordingly, such cleaning agentscannot be applied to modern microelectronic devices having finepatterns.

SUMMARY

An object of the present invention is to provide a cleaning agent for amicroelectronic device provided with metal wiring (e.g., tungsten,tungsten alloy, copper or copper alloy), which has an excellent abilityto remove material (e.g., abrasive grains in a CMP slurry such asalumina and silica, an iron nitrate aqueous solution added to acceleratepolishing, an anticorrosive added to suppress corrosion of a wiringmetal, and residues of a metal wiring and zinc and magnesium metals usedon a side of the metal wiring) that remains on a wafer subsequent to aCMP step without corroding the metal wiring.

Namely, the present invention is a cleaning agent for post-CMP cleaningof a microelectronic device in which a metal wiring is formed, whereinthe metal wiring comprising copper or tungsten. In one aspect, thecleaning agent comprises an organic amine (A), a quaternary ammoniumhydroxide (B), a chelating agent (C), and water (W), and has a pH of 7.0to 14.0. In another aspect, the cleaning agent comprises a cyclicpolyamine (A1) and/or a cyclic polyamine (A2), a polyphenol basedreducing agent (B) having 2 to 5 hydroxyl groups, a quaternary ammoniumhydroxide (C), ascorbic acid (D), and water.

The cleaning agent for a microelectronic device provided with tungstenor tungsten alloy wiring has an excellent ability to remove abrasivegrains derived from a polishing slurry, an excellent ability to removemetallic residues from an insulating layer, and excellentanticorrosiveness to the tungsten wiring.

The cleaning agent for a microelectronic device provided with copper orcopper alloy wiring has an excellent ability to remove abrasive grainsderived from a polishing slurry, an excellent ability to remove metallicresidues from an insulating layer, and excellent anticorrosiveness tothe copper wiring.

Moreover, a microelectronic device having good contact resistancewithout shorting is easily obtained using the cleaning agents describedherein at the step subsequent to the CMP step in the manufacturingprocess of the microelectronic device.

Other aspects, features and advantages will be more fully apparent fromthe ensuing disclosure and appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

For ease of reference, “microelectronic device” corresponds tosemiconductor substrates, flat panel displays, phase change memorydevices, solar panels and other products including solar substrates,photovoltaics, and microelectromechanical systems (MEMS), manufacturedfor use in microelectronic, integrated circuit, or computer chipapplications. Solar substrates include, but are not limited to, silicon,amorphous silicon, polycrystalline silicon, monocrystalline silicon,CdTe, copper indium selenide, copper indium sulfide, and galliumarsenide on gallium. The solar substrates may be doped or undoped. It isto be understood that the term “microelectronic device” is not meant tobe limiting in any way and includes any substrate that will eventuallybecome a microelectronic device or microelectronic assembly.

As used herein, “material” corresponds to post-CMP residue and/orcontaminants. As used herein, “contaminants” correspond to chemicalspresent in the CMP slurry, reaction by-products of the polishing slurry,and any other materials that are the by-products of the CMP process,including but not limited to, an iron nitrate aqueous solution added toaccelerate polishing, and an anticorrosive added to suppress corrosionof a wiring metal. As used herein, “post-CMP residue” corresponds toparticles from the polishing slurry, e.g., silica-containing particles,alumina-containing particles, residues of a metal wiring and zinc andmagnesium metals used on a side of the metal wiring, chemicals presentin the slurry, reaction by-products of the polishing slurry, carbon-richparticles, polishing pad particles, brush deloading particles, equipmentmaterials of construction particles, copper, copper oxides, organicresidues, and any other materials that are the by-products of the CMPprocess.

In a first aspect, a first composition useful for the removal ofmaterial remaining on a microelectronic device subsequent to CMP isdescribed, said first composition comprising, consisting of, orconsisting essentially of an organic amine (A), a quaternary ammoniumhydroxide (B), a chelating agent (C), and water (W), wherein thecleaning agent has a pH of 7.0 to 14.0. The first composition isparticularly useful for the removal of material remaining on amicroelectronic device comprising tungsten or tungsten alloy, preferablysubsequent to the CMP of tungsten or tungsten alloy layers.

Examples of the organic amine (A) include chain amines, cyclic amines,or any combination thereof. Examples of the chain amines include chainmonoamines, chain polyamines, or any combination thereof. Examples ofthe chain monoamines include chain alkyl monoamines having 1 to 6 carbonatoms, and chain alkanolamines having 2 to 6 carbon atoms (A1). Examplesof the chain alkylamines having 1 to 6 carbon atoms include alkylamines(e.g., methylamine, ethylamine, propylamine, isopropylamine, butylamine,hexylamine), dialkylamines (e.g., dimethylamine, ethylmethylamine,propylmethylamine, butylmethylamine, diethylamine, propylethylamine,diisopropylamine), trialkylamines (e.g., trimethylamine,ethyldimethylamine, diethylmethylamine, triethylamine,tri-n-propylamine, tri-n-butylamine), or any combination thereof.Examples of the chain alkanolamines having 2 to 6 carbon atoms (A1)include monoethanolamine (MEA), diethanolamine, triethanolamine,dimethylaminoethanol, diethylaminoethanol, 2-amino-2-methyl-1-propanol,N-(aminoethyl)ethanolamine, N,N-dimethyl-2-aminoethanol,2-(2-aminoethoxy)ethanol, or any combination thereof. Examples of thechain polyamines (A2) include alkylene diamines having 2 to 5 carbonatoms, polyalkylene polyamines having 2 to 6 carbon atoms, or anycombination thereof. Examples of the alkylene diamines having 2 to 5carbon atoms include ethylenediamine, propylenediamine,trimethylenediamine, tetramethylenediamine, hexamethylenediamine, or anycombination thereof. Examples of diamines having an alkyl groupsubstituted by a hydroxyl group include 2-hydroxyethylaminopropylamineand diethanolaminopropylamine. Examples of polyalkylene polyamineshaving 2 to 6 carbon atoms include diethylenetriamine,triethylenetetramine, tetraethylenepentamine (TEP),hexamethyleneheptamine, iminobispropylamine, bis(hexamethylene)triamine,pentaethylenehexamine, or any combination thereof. Examples of thecyclic amines include aromatic amines and alicyclic amines, andspecifically include C6 to C20 aromatic amines (e.g., aniline,phenylenediamine, tolylenediamine, xylylenediamine, methylenedianiline,diphenyletherdiamine, naphthalenediamine, anthracenediamine); C4 to C15alicyclic amines (e.g., isophoronediamine, and cyclohexylenediamine); C4to C15 heterocyclic amines (e.g., piperazine, N-aminoethylpiperazine,and 1,4-diaminoethylpiperazine), or any combination thereof.

Of these organic amines (A), an alkanolamine (A1) represented by thefollowing general formula (1) and a chain polyamine (A2) represented bythe following general formula (2) are preferable from the viewpoint ofanticorrosiveness to tungsten and an ability to remove abrasive grains.From the viewpoint of an ability to remove metallic residues, the chainpolyamines are more preferable, and tetraethylenepentamine isparticularly preferable.

wherein R¹ to R³ each independently represent a hydrogen atom or analkyl group that may be partially substituted by a hydroxyl group; andat least one of R¹ to R³ represents an alkyl group substituted by ahydroxyl group.

wherein R⁴ to R⁸ each independently represent a hydrogen atom or analkyl group that may be partially substituted by a hydroxyl group; Y¹and Y² each independently represent an alkylene group; and n represents0 or an integer of 1 to 2.

From the viewpoint of an ability to remove metals and anticorrosivenessto tungsten, the content of the organic amine (A) used in the firstcomposition useful for removing material from a microelectronic deviceprovided with tungsten wiring is 0.01 to 0.3% by weight, based on thetotal weight of the first composition. The content of the organic amine(A) is preferably 0.03 to 0.25% by weight, more preferably 0.05 to 0.2%by weight, and particularly preferably 0.07 to 0.15% by weight, based onthe total weight of the first composition.

Examples of the quaternary ammonium hydroxide (B) includetetraalkylammonium salts, trialkylhydroxyalkylammonium salts,dialkyl-bis(hydroxyalkyl)ammonium salts, tris(hydroxyalkyl)alkylammoniumsalts, or any combination thereof. Of these quaternary ammoniumhydroxides (B), the quaternary ammonium hydroxide (B1) represented bythe following general formula (3) is preferable from the viewpoint of anability to remove abrasive grains.

wherein R⁹ to R¹² each independently represent an alkyl group having 1to 3 carbon atoms and that may be partially substituted by a hydroxylgroup. Specific examples thereof include tetraalkylammonium hydroxide,(hydroxyalkyl)trialkylammonium hydroxide,bis(hydroxyalkyl)dialkylammonium hydroxide, andtris(hydroxyalkyl)alkylammonium hydroxide. From the viewpoint ofanticorrosiveness to tungsten, tetraalkylammonium hydroxide and(hydroxyalkyl)trialkylammonium hydroxide are preferable,tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide(TEAH), and (hydroxyethyl)trimethylammonium hydroxide(choline) are morepreferable, and tetramethylammonium hydroxide is particularlypreferable.

From the viewpoint of an ability to remove abrasive grains andanticorrosiveness to tungsten, the content of the quaternary ammoniumhydroxide (B) used in the first composition useful for removing materialfrom a microelectronic device provided with tungsten wiring is 0.005 to10% by weight, based on the total weight of the first composition. Thecontent of the quaternary ammonium hydroxide (B) is preferably 0.01 to2% by weight, and more preferably 0.02 to 1% by weight, based on thetotal weight of the first composition.

From the viewpoint of an ability to remove metallic residues and anability to remove abrasive grains, a molar ratio of the quaternaryammonium hydroxide (B) to the organic amine (A), (B)/(A), is preferably0.1 to 5.0, and more preferably 0.5 to 2.0.

Examples of the chelating agent (C) include phosphorus based chelatingagents (C1), amine based chelating agents (C2), aminocarboxylic acidbased chelating agents (C3), carboxylic acid based chelating agents(C4), ketone based chelating agents (C5), polymer chelating agents (C6),or any combination thereof. Examples of the phosphorus based chelatingagents (C1) include sodium pyrophosphate, sodium tripolyphosphate,potassium trimetaphosphate, sodium tetrametaphosphate,1-hydroxyethylidene-1,1-diphosphonic acid, or any combination thereof.Examples of the amine based chelating agents (C2) includeethylenediamine, triethylenetetramine, tetraethylenepentamine,dimethylglyoxime, 8-oxyquinoline, porphyrin, or any combination thereof.Examples of the aminocarboxylic acid based chelating agents (C3) includeethylenediamine diacetate and neutralized products of metal saltsthereof (the metal is sodium, and potassium, for example),ethylenediamine tetraacetate (EDTA) and neutralized products of metalsalts thereof, hexylenediamine diacetate and neutralized products ofmetal salts thereof, hydroxyethylimino diacetate and neutralizedproducts of metal salts thereof, trisodium nitrilotriacetate, trisodiumhydroxyethylethylenediaminetriacetate (HEDTA), pentasodiumdiethylenetriaminepentaacetate, hexasodiumtriethylenetetraminehexaacetate, dihydroxyethyl glycine, glycine,tetrasodium L-glutamate diacetate, or any combination thereof. Examplesof the carboxylic acid based chelating agents (C4) include oxalic acid,disodium malate, ethylene dicarboxylic acid, adipic acid, sebacic acid,gluconic acid, sodium gluconate, or any combination thereof. Examples ofthe ketone based chelating agents (C5) include acetylacetone,hexane-2,4-dione, 3-ethylnonane-4,7-dione, or any combination thereof.Examples of the polymers chelating agents (C6) include sodiumpolyacrylate and poly[2-hydroxyacrylate sodium].

Of these chelating agents (C), from the viewpoint of an ability toremove metallic residues, the amine based chelating agents (C2), theaminocarboxylic acid based chelating agents (C3), and the carboxylicacid based chelating agents (C4) are preferable, and the aminocarboxylicacid based chelating agents (C3) are more preferable. Of theaminocarboxylic acid based chelating agents (C3), ethylenediaminetetraacetate, hexylenediamine diacetate, and hydroxyethylimino diacetateare particularly preferable.

From the viewpoint of anticorrosiveness to tungsten and an ability toremove metallic residues, the content of the chelating agent (C) used inthe first composition useful for removing material from amicroelectronic device provided with tungsten wiring is 0.0001 to 0.2%by weight, based on the total weight of the first composition. Thecontent of the chelating agent (C) is preferably 0.0005 to 0.1% byweight, and particularly preferably 0.001 to 0.05% by weight, based onthe total weight of the first composition.

From the viewpoint of anticorrosiveness to tungsten and an ability toremove metallic residues, a molar ratio of the chelating agent (C) tothe organic amine (A), (C)/(A), is preferably 0.001 to 5, morepreferably 0.003 to 3, and particularly preferably 0.005 to 1.

In the first composition useful for removing material from amicroelectronic device provided with tungsten wiring, water (W) ispresent, preferably water having low conductivity (μS/cm; 25° C.).Specifically, the conductivity thereof is usually about 0.055 to about0.2, preferably about 0.056 to about 0.1, and more preferably about0.057 to about 0.08 from the viewpoint of an ability to remove metallicresidues, availability, and prevention of the tungsten wiring fromrecontamination (i.e., reattachment of metal ions in the composition tothe tungsten wiring). Ultrapure water is preferable.

The pH at 25° C. of the first composition is about 7.0 to about 14.0.From the viewpoint of an ability to remove abrasive grains andanticorrosiveness to tungsten, pH of about 10.0 to about 13.5 ispreferable, and pH of about 12.0 to about 13.0 is more preferable.

Other than the organic amine (A), the quaternary ammonium hydroxide (B),the chelating agent (C), and water (W), a surface active agent (E1), areducing agent (E2), and combinations thereof may be added as additionalcomponents (E) when necessary to the first composition for cleaning amicroelectronic device provided with a tungsten wiring.

The surface active agent (E1) is preferably added to remove metallicresidues and abrasive grains. Examples of such a surface active agentinclude nonionic surface active agents, anionic surface active agents,cationic surface active agents, amphoteric surface active agents, or anycombination thereof. When present, the content of the surface activeagent may be an amount necessary to reduce surface tension of thecleaning agent, and is usually 0.0001 to 1% by weight based on theweight of the first composition, preferably 0.001 to 0.1% by weight, andparticularly preferably 0.001 to 0.01% by weight.

Examples of the reducing agent (E2) include organic reducing agents,inorganic reducing agents, or any combination thereof. Examples of theorganic reducing agents include polyphenol based reducing agents such ascatechol, hydroquinone, gallic acid, oxalic acid and salts thereof, C6to C9 aldehydes, or any combination thereof. Examples of the inorganicreducing agents include sulfurous acid and salts thereof, andthiosulfuric acid and salts thereof. Of these reducing agents, theorganic reducing agents are preferable from the viewpoint ofanticorrosiveness to tungsten, the polyphenol based reducing agents aremore preferable, and gallic acid is particularly preferable. Whenpresent, the content of the reducing agent is usually 0.0001 to 1.0% byweight, more preferably 0.001 to 0.5% by weight, and particularlypreferably 0.01 to 0.1% by weight, based on the weight of the firstcomposition.

In a particularly preferred embodiment, the first composition comprises,consists of, or consists essentially of TMAH, TEP, EDTA and water.

The first composition useful for removing material from amicroelectronic device provided with tungsten wiring is obtained bymixing the organic amine (A), the quaternary ammonium hydroxide (B), thechelating agent (C), and other components (E) when necessary, with water(W). A method for mixing the individual components is not particularlylimited. From the viewpoint of easy and uniform mixing in a short timeor the like, however, a method for mixing water (W) with the organicamine (A) and the quaternary ammonium hydroxide (B), and then mixing thechelating agent (C) and other components (E), when present, ispreferable. A stirrer, a dispersion machine, or the like can be used asa mixing apparatus. Examples of the stirrer include mechanical stirrersand magnetic stirrers. Examples of the dispersion machine includehomogenizers, ultrasonic dispersion machines, ball mills, and beadmills.

It should be appreciated that the first composition can be useful toremoval material from a microelectronic device comprising tungsten ortungsten alloy wiring, as well as microelectronic devices having awiring made of a different metal such as a copper wiring, aluminumsubstrates for recording medium magnetic disks, glassy carbonsubstrates, glass substrates, ceramic substrates, glass substrates forliquid crystals, glass substrates for solar cells, and the like.Preferably, the first composition is used to remove material after CMPof a surface comprising tungsten or tungsten wiring because iteffectively removes metal residues and abrasive grains.

It should further be appreciated that the first composition can beprovided in a concentrated form that can be diluted to the preferredconcentrations at the point of use.

In a second aspect, a method of removing material from a microelectronicdevice comprising tungsten or tungsten alloy is described, said methodcomprising contacting a surface of the microelectronic device with acomposition under conditions useful for removing material from thesurface. Preferably, the composition is the first composition describedherein.

In a third aspect, a second composition useful for the removal ofmaterial remaining on a microelectronic device subsequent to CMP isdescribed, said second composition comprising, consisting of, orconsisting essentially of: a cyclic polyamine (P) represented by thefollowing general formula (1) (P1) and/or a cyclic polyamine representedby the following general formula (2) (P2); a polyphenol based reducingagent (R) having 2 to 5 hydroxyl groups; a quaternary ammonium hydroxide(Q); ascorbic acid (AA); and water (W). The second composition isparticularly useful for the removal of material remaining on amicroelectronic device comprising copper or copper alloy, preferablysubsequent to the CMP of copper or copper alloy layers.

Examples of the cyclic polyamine include a cyclic polyamine (P1)represented by the following general formula (4) and a cyclic polyamine(P2) represented by the following general formula (5).

wherein, R¹ represents a hydrogen atom, an alkyl group, an amino alkylgroup, or a hydroxyalkyl group; and R² represents an alkyl group, anamino alkyl group, or a hydroxyalkyl group.

wherein, R³ represents an amino alkyl group.

Examples of the cyclic polyamine (P1) include a cyclic polyamine (P11)having an hydrogen atom at the R¹ position and an alkyl group at the R²position in the above general formula (4); a cyclic polyamine (P12)having an amino alkyl group or a hydroxyalkyl group; a cyclic polyamine(P13) having an alkyl group at both of the R¹ position and the R²position; a cyclic polyamine (P14) having an alkyl group at the R¹position and an amino alkyl group or a hydroxyalkyl group at the R²position; and a cyclic polyamine (P15) having an amino alkyl group or ahydroxyalkyl group at the R¹ position and an amino alkyl group or ahydroxyalkyl group at the R² position. Alternatively, a cyclic polyamine(P11) having an hydrogen atom at the R¹ position and an alkyl group atthe R² position in the above general formula (4); a cyclic polyamine(P12) having an amino alkyl group or a hydroxyalkyl group at the R¹position or the R² position; a cyclic polyamine (P13) having an alkylgroup at both of the R¹ position and the R² position; a cyclic polyamine(P14) having an alkyl group at the R¹ position and an amino alkyl groupor a hydroxyalkyl group at the R² position; and a cyclic polyamine (P15)having an amino alkyl group at the R¹ position and an amino alkyl groupat the R² position.

Examples of the cyclic polyamine (P11) include N-methylpiperazine,N-ethylpiperazine, and N-isobutylpiperazine. Examples of the cyclicpolyamine (P12) include N-aminomethylpiperazine, N-aminoethylpiperazine,N-aminopropylpiperazine, N-hydroxymethylpiperazine,N-hydroxyethylpiperazine, and N-hydroxypropylpiperazine. Examples of thecyclic polyamine (P13) include 1,4-dimethylpiperazine,1,4-diethylpiperazine, 1,4-diisopropylpiperazine, and1,4-dibutylpiperazine. Examples of the cyclic polyamine (P14) include1-aminomethyl-4-methylpiperazine, 1-hydroxymethyl-4-methylpiperazine,1-aminoethyl-4-ethylpiperazine, and 1-hydroxyethyl-4-ethylpiperazine.Examples of the cyclic polyamine (P15) include1,4-(bisaminoethyl)piperazine, 1,4-(bishydroxyethyl)piperazine,1,4-(bisaminopropyl)piperazine, 1,4-(bishydroxypropyl)piperazine,1-aminoethyl-4-hydroxyethylpiperazine, and1-aminopropyl-4-hydroxypropylpiperazine.

Examples of the cyclic polyamine (P12) include those having an aminoalkyl group with 2 to 4 carbon atoms at the R³ position in the abovegeneral formula (5). Specifically, examples thereof includeN-aminoethylmorpholine, N-aminopropylmorpholine, andN-aminoisobutylmorpholine.

Of these cyclic polyamines, the cyclic polyamine (P12) having an aminoalkyl group or a hydroxyalkyl group at the R¹ position or the R²position in the above general formula (4), the cyclic polyamine (P14),the cyclic polyamine (P15), and the cyclic polyamine (P2) having anamino alkyl group at the R³ position in the above general formula (5)are preferable from the viewpoint of anticorrosiveness to the copperwiring and an ability to remove organic residues that remain on thewafer after the CMP process.

From the viewpoint of an ability to remove the abrasive grains thatremain on the wafer after the CMP process, the cyclic polyamine (P)having an amino alkyl group at the R¹ or R² position in the abovegeneral formula (4) is more preferable. N-aminoalkylpiperazine and1,4-(bisaminoalkyl)piperazine having 1 to 3 carbon atoms in the aminoalkyl group are particularly preferable.

From the viewpoint of anticorrosiveness to the copper wiring and anability to remove organic residues, the content of the cyclic polyamine(P) in the second composition is usually 0.001 to 5% by weight,preferably 0.005 to 2% by weight, more preferably 0.01 to 1% by weight,and particularly preferably 0.01 to 0.5% by weight based on the totalweight of the second composition.

The polyphenol based reducing agent (R) having 2 to 5 hydroxyl groups isa compound including a phenol skeleton having 2 to 5 hydroxyl groupsbonded to a benzene ring, an aromatic ring, or the like, and may includeanother functional groups such as a carboxyl group. Examples of thepolyphenol based reducing agent having two hydroxyl groups includecatechol, caffeic acid, alizarin, endocrocin, urushiol, flavone,resorcinol, and hydroquinone. Examples of the polyphenol based reducingagent having three hydroxyl groups include emodin, pyrogallol, andgallic acid. Examples of the polyphenol based reducing agent having fouror five hydroxyl groups include quercetin, catechin, and anthocyanin.

Of these reducing agents (R), the polyphenol based reducing agent having3 to 5 hydroxyl groups is preferable from the viewpoint ofanticorrosiveness to the copper wiring. From the viewpoint of chemicalstability over time in the second composition, gallic acid, pyrogallol,and catechin are more preferable. Further, gallic acid having a carboxylgroup in the molecule is particularly preferable from the viewpoint ofan ability to remove metallic residues.

From the viewpoint of anticorrosiveness to the copper wiring and anability to remove metallic residues, the content of the polyphenol basedreducing agent (R) having 2 to 5 hydroxyl groups is usually 0.001 to 5%by weight, preferably 0.001 to 2% by weight, more preferably 0.01 to 1%by weight, and particularly preferably 0.05 to 0.5% by weight based onthe total weight of the second composition.

Examples of the quaternary ammonium hydroxide (Q) include salts composedof a hydroxy anion and a cation having a hydrocarbon group bonded to aquaternary nitrogen atom. Examples of the hydrocarbon group bonded to aquaternary nitrogen atom include an alkyl group, an alkenyl group, anallyl group, an aralkyl group, and a hydrocarbon group that an alkylgroup, an alkenyl group, an allyl group or an aralkyl group is partiallysubstituted by a hydroxyl group. Preferable examples thereof include aquaternary ammonium hydroxide (Q1) represented by the following formula(6).

wherein R⁴ to R⁷ each independently represent an alkyl group having 1 to4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms.

Specific examples include tetraalkylammonium salts having an alkyl groupwith 1 to 4 carbon atoms or a hydroxyalkyl group with 1 to 4 carbonatoms, trialkyl-hydroxyalkylammonium salts having an alkyl group with 1to 4 carbon atoms or a hydroxyalkyl group with 1 to 4 carbon atoms,dialkyl-bis(hydroxyalkyl)ammonium salts having an alkyl group with 1 to4 carbon atoms or a hydroxyalkyl group with 1 to 4 carbon atoms, andtris(hydroxyalkyl)alkylammonium salts having an alkyl group with 1 to 4carbon atoms or a hydroxyalkyl group with 1 to 4 carbon atoms.

Of these quaternary ammonium hydroxides (Q), tetraalkylammoniumhydroxide, (hydroxyalkyl)trialkylammonium hydroxide,bis(hydroxyalkyl)dialkylammonium hydroxide, andtris(hydroxyalkyl)alkylammonium hydroxide are preferable from theviewpoint of an ability to remove organic residues. From the viewpointof anticorrosiveness to the copper wiring, tetraalkylammonium hydroxideand (hydroxyalkyl)trialkylammonium hydroxide are preferable.Tetramethylammonium hydroxide, tetraethylammonium hydroxide, and(hydroxyethyl)trimethylammonium hydroxide(choline) are more preferable,and tetramethylammonium hydroxide is particularly preferable.

From the viewpoint of an ability to remove organic residues andanticorrosiveness to the copper wiring, the content of the quaternaryammonium hydroxide (Q) is usually 0.01 to 10% by weight, preferably 0.02to 5% by weight, and more preferably 0.05 to 2% by weight based on thetotal weight of the second composition.

The second composition contains ascorbic acid (AA), specifically,L-(+)-ascorbic acid and D-(+)-ascorbic acid (called erythorbic acid by acommon name). The ascorbic acid (AA) has a function to suppressoxidization of the polyphenol based reducing agent (R) having 2 to 5hydroxyl groups, and a function to improve an ability to remove metallicresidues.

From the viewpoint of anticorrosiveness to the copper wiring and anability to remove metallic residues, the content of the ascorbic acid(AA) is usually 0.01 to 5% weight, preferably 0.05 to 3% by weight, morepreferably 0.1 to 2% by weight, and particularly preferably 0.1 to 1% byweight based on the total weight of the second composition.

The second composition further contains water. Preferably, the water haslow conductivity (μS/cm; 25° C.). Specifically, the conductivity thereofis usually about 0.055 to about 0.2, preferably about 0.056 to about0.1, and more preferably about 0.057 to about 0.08 from the viewpoint ofan ability to remove organic residues and metallic residues,availability, and prevention of the copper wiring from recontamination(reattachment of metal ions in the water to the copper wiring).Ultrapure water is preferable.

From the viewpoint of an ability to remove organic residues, an abilityto remove metallic residues, and viscosity of the solution, the contentof water is usually 69.0 to 99.9% by weight, preferably 79.0 to 99.5% byweight, more preferably 89.0 to 99.0% by weight, and particularlypreferably 92.0 to 99.0% by weight based on the total weight of thesecond composition.

Other than the cyclic polyamine (P), the polyphenol based reducing agent(R) having 2 to 5 hydroxyl groups, the quaternary ammonium hydroxide(Q), the ascorbic acid (AA), and water (W) as the essential components,a surface active agent (E1), a reducing agent (R2) other than thepolyphenol based reducing agent (R) having 2 to 5 hydroxyl groups, acomplexing agent (E3), a corrosion inhibitor (E4), and combinationsthereof, may be added as additional components when necessary to thesecond composition for the removal of material from a microelectronicdevice comprising copper.

Examples of useful surface active agents (E1) were described herein inthe first aspect.

Examples of the reducing agent (R2) other than the polyphenol basedreducing agent (R) having 2 to 5 hydroxyl groups include organicreducing agents and inorganic reducing agents. Examples of the organicreducing agent include phenol compounds and benzaldehydes having onehydroxyl group and 6 to 30 carbon atoms such as oxalic acid and saltsthereof, hydrogen oxalate and salts thereof, and aldehydes having 6 to 9carbon atoms. Examples of the inorganic reducing agent include sulfurousacid and salts thereof, and thiosulfuric acid and salts thereof.

From the viewpoint of water solubility and anticorrosiveness to thecopper wiring, of these reducing agents (R2), the organic reducingagents are preferable, aliphatic organic reducing agents are morepreferable, and oxalic acid and salts thereof are particularlypreferable. Moreover, from the viewpoint of complexing action, oxalatesalts are preferable and ammonium oxalate is more preferable.

The content of the reducing agent (R2) is usually 0.001 to 1.0% byweight, more preferably 0.01 to 0.5% by weight, and particularlypreferably 0.05 to 0.1% by weight based on the weight of the secondcomposition from the viewpoint of improving anticorrosiveness to thecopper wiring. In the case where the content of these reducing agents,i.e., the reducing agent other than the polyphenol based reducing agenthaving 2 to 5 hydroxyl groups exceeds 1.0% by weight, anticorrosivenessto the copper wiring is decreased instead.

Examples of the complexing agent (E3) include aromatic and aliphatichydroxycarboxylic acids having 1 to 6 carbon atoms (and salts thereof),heterocyclic compounds having at least one of a hydroxyl group having 9to 23 carbon atoms and a carboxyl group having 9 to 23 carbon atoms, andphosphonic acids having 6 to 9 carbon atoms (and salts thereof). Ofthese complexing agents (E3), from the viewpoint of improvinganticorrosiveness to the copper wiring, an aliphatic hydroxycarboxylicacid (or a salt thereof) and a polycarboxylic acid (or a salt thereof)are preferable, and an aliphatic hydroxycarboxylic acid (or a saltthereof) are particularly preferable.

In the case of adding the complexing agent, the content of thecomplexing agent (E3) is usually 0.001 to 0.5% by weight, preferably0.01 to 0.3% by weight, and particularly preferably 0.05 to 0.1% byweight based on the weight of the second composition from the viewpointof improving anticorrosiveness to the copper wiring.

Suitable corrosion inhibitors (E4) include, but are not limited to,ribosylpurines such as N-ribosylpurine, adenosine, guanosine,2-aminopurine riboside, 2-methoxyadenosine, and methylated or deoxyderivatives thereof, such as N-methyladenosine (C₁₁H₁₅N₅O₄),N,N-dimethyladenosine (C₁₂H₁₇N₅O₄), trimethylated adenosine(C₁₃H₁₉N₅O₄), trimethyl N-methyladenosine (C₁₄H₂₁N₅O₄),C-4′-methyladenosine, and 3-deoxyadenosine; degradation products ofadenosine and adenosine derivatives including, but not limited to,adenine (C₅H₅N₅), methylated adenine (e.g., N-methyl-7H-purin-6-amine,C₆H₇N₅), dimethylated adenine (e.g., N,N-dimethyl-7H-purin-6-amine,C₇H₉N₅), N4,N4-dimethylpyrimidine-4,5,6-triamine (C₆H₁₁N₅),4,5,6-triaminopyrimidine, allantoin (C₄H₆N₄O₃), hydroxylated C—O—O—Cdimers ((C₅H₄N₅O₂)₂), C—C bridged dimers ((C₅H₄N₅)₂ or (C₅H₄N₅O)₂),ribose (C₅H₁₀O₅), methylated ribose (e.g.,5-(methoxymethyl)tetrahydrofuran-2,3,4-triol, C₆H₁₂O₅), tetramethylatedribose (e.g., 2,3,4-trimethoxy-5-(methoxymethyl)tetrahydrofuran,C₉H₁₈O₅), and other ribose derivatives such as methylated hydrolyzeddiribose compounds; purine-saccharide complexes including, but notlimited to, xylose, glucose, etc.; other purine compounds such aspurine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uricacid, and isoguanine, and methylated or deoxy derivatives thereof;triaminopyrimidine and other substituted pyrimidines such asamino-substituted pyrimidines; dimers, trimers or polymers of any of thecompounds, reaction or degradation products, or derivatives thereof; andcombinations thereof. For example, the corrosion inhibitors may compriseat least one species selected from the group consisting ofN-ribosylpurine, 2-aminopurine riboside, 2-methoxyadenosine,N-methyladenosine, N,N-dimethyladenosine, trimethylated adenosine,trimethyl N-methyladenosine, C-4′-methyladenosine, 3-deoxyadenosine;methylated adenine, dimethylated adenine,N4,N4-dimethylpyrimidine-4,5,6-triamine, 4,5,6-triaminopyrimidine,hydroxylated C—O—O—C dimers, C—C bridged dimers, ribose, methylatedribose, tetramethylated ribose, xylose, glucose, isoguanine,triaminopyrimidine, amino-substituted pyrimidines, and combinationsthereof. Alternatively, the corrosion inhibitors may include at leastone species selected from the group consisting of 2-methoxyadenosine,N-methyladenosine, N,N-dimethyladenosine, trimethylated adenosine,trimethyl N-methyladenosine, C-4′-methyladenosine, 3-deoxyadenosine andcombinations thereof.

In a particularly preferred embodiment, the second compositioncomprises, consists of, or consists essentially of TMAH,N-aminoethylpiperazine (AEP), ascorbic acid, gallic acid, adenosine, andwater.

In a particularly preferred embodiment, the second composition issubstantially devoid of abrasive (prior to cleaning), aminotetrazole,and fluoride. “Substantially devoid” is defined herein as less than 2wt. %, preferably less than 1 wt. %, more preferably less than 0.5 wt.%, most preferably less than 0.1 wt. %, and most preferably 0 wt %,based on the total weight of the composition.

The second composition can be produced by mixing the cyclic polyamine(P), the polyphenol based reducing agent (R) having 2 to 5 hydroxylgroups, the quaternary ammonium hydroxide (Q), the ascorbic acid (AA),and other components when present, with water. A method for mixing theseis not particularly limited. From the viewpoint of easy and uniformmixing in a short time or the like, however, a method for mixing waterand the polyphenol based reducing agent (R) having 2 to 5 hydroxylgroups with the ascorbic acid (AA), and then mixing the cyclic polyamine(P), the quaternary ammonium hydroxide (Q) and other components whennecessary is preferable. The temperature and time during performinguniform mixing are not limited, and can be determined properly accordingto the scale, equipment, and the like for production.

A stirrer or a dispersion machine can be used as a mixing apparatus.Examples of the stirrer include mechanical stirrers and magneticstirrers. Examples of the dispersion machine include homogenizers,ultrasonic dispersion machines, ball mills, and bead mills.

It should be appreciated that the second composition can be useful toremoval material from a microelectronic device comprising copper orcopper alloy wiring, as well as microelectronic devices having a wiringmade of a different metal such as a copper wiring, copper platedsubstrates for semiconductor cleaning evaluation, aluminum substratesfor recording medium magnetic disks, glassy carbon substrates, glasssubstrates, ceramic substrates, glass substrates for liquid crystals,glass substrates for solar cells, and the like. Preferably, the secondcomposition is used to remove material after CMP of a surface comprisingcopper or copper wiring because it effectively removes metal residuesand abrasive grains.

It should further be appreciated that the second composition can beprovided in a concentrated form that can be diluted to the preferredconcentrations at the point of use.

In a fourth aspect, a method of removing material from a microelectronicdevice comprising copper or copper alloy is described, said methodcomprising contacting a surface of the microelectronic device with acomposition under conditions useful for removing material from thesurface. Preferably, the composition is the second composition describedherein.

Examples of the cleaning method for removing material from amicroelectronic device having a metal wiring include a single wafermethod and a batch method. The single wafer method is a method forcleaning one microelectronic device at a time using a brush by rotatingthe microelectronic device while injecting the appropriate composition.The batch method is a method for cleaning several microelectronicdevices by soaking the microelectronic devices in the appropriatecomposition.

In yet another aspect, the first and second compositions can be usedduring a cleaning step after resist development, after dry etching,after wet etching, after dry ashing, after resist removing, before andafter the CMP treatment, and before and after the CVD treatment in theprocess in which a microelectronic device having a metal wiring isproduced.

EXAMPLES

Hereinafter, compositions and methods will be further described usingExamples and Comparative Examples, but the present invention will not belimited to these. Hereinafter, % means % by weight and parts means partsby weight unless otherwise specified.

Hereinafter, preparation of a cleaning agent for a semiconductorprovided with a tungsten wiring according to Examples 1 to 5 andComparative Examples 1 to 4 will be described.

Example 1

0.14 parts of TEP (A-1) (trade name: AFR-AN6, purity of 99.2%, made byTosoh Corporation), 0.240 parts of a 25% TMAH aqueous solution (B-1)(trade name: 25% TMAH solution, an aqueous solution with purity of 25%,made by Tama Chemicals Co., Ltd.), 0.002 parts of ethylenediaminetetraacetate (C-1) (trade name: Chelest 3A, purity of 98.0%, made byChelest Corporation) were added to a 300-ml container made ofpolyethylene. Then, 99.8 parts of water (W) was added so that the totalweight was 100 parts. The solution was stirred by a magnetic stirrer toobtain a first composition for removing material from a microelectronicdevice comprising tungsten wiring (D-1). The pH of the obtained cleaningagent was 13.2.

Example 2

The same operation as that in Example 1 was performed except that 0.14parts of MEA (A-2) (purity of 99%, made by Wako Pure ChemicalIndustries, Ltd.) was used instead of (A-1) in Example 1, the blendingamount of (B-1) was changed to 0.200 parts, the blending amount of (C-1)was changed to 0.004 parts, and water was added so that the total weightwas 100 parts. Thereby, a first composition for removing material from amicroelectronic device comprising tungsten wiring (D-2) was obtained.The pH of the obtained cleaning agent was 12.5.

Example 3

The same operation as that in Example 1 was performed except that a 25%TEAH aqueous solution (B-2) (trade name: 25% TEAH solution, an aqueoussolution with purity of 25%, made by Wako Pure Chemical Industries,Ltd.) was used instead of (B-1) in Example 1. Thereby, a firstcomposition for removing material from a microelectronic devicecomprising tungsten wiring (D-3) was obtained. The pH of the obtainedcleaning agent was 12.4.

Example 4

The same operation as that in Example 1 was performed except thathydroxyethylethylenediamine triacetate (C-2) (purity of 98.0%, made byWako Pure Chemical Industries, Ltd.) was used instead of (C-1) inExample 1, and the blending amount thereof was 0.004 parts. Thereby, afirst composition for removing material from a microelectronic devicecomprising tungsten wiring (D-4) was obtained. The pH of the obtainedcleaning agent was 12.9.

Example 5

The same operation as that in Example 1 was performed except that theblending amount of (A-1) in Example 4 was changed to 0.07 parts, theblending amount of (B-1) in Example 4 was changed to 0.08 parts, theblending amount of (C-1) in Example 4 was changed to 0.006 parts, andwater was added so that the total weight was 100 parts. Thereby, a firstcomposition for removing material from a microelectronic devicecomprising tungsten wiring (D-5) was obtained. The pH of the obtainedcleaning agent was 9.2.

Comparative Example 1

The same operation as that in Example 1 was performed except that (A-1)in Example 1 was not added. Thereby, a comparative composition forremoving material from a microelectronic device comprising tungstenwiring (D′-1) was obtained. The pH of the obtained cleaning agent was10.4.

Comparative Example 2

The same operation as that in Example 1 was performed except that (B-1)in Example 1 was not added. Thereby, a comparative composition forremoving material from a microelectronic device comprising tungstenwiring (D′-2) was obtained. The pH of the obtained cleaning agent was9.1.

Comparative Example 3

The same operation as that in Example 1 was performed except that (C-1)in Example 1 was not added. Thereby, a comparative composition forremoving material from a microelectronic device comprising tungstenwiring (D′-3) was obtained. The pH of the obtained cleaning agent was13.4.

Comparative Example 4

The same operation as that in Example 1 was performed except that 0.100parts of ethylenediamine tetraacetate (C-1) and 5.00 parts of oxalicacid (purity of 99%, made by Wako Pure Chemical Industries, Ltd.) wereadded, and then water was added so that the total weight was 100 parts.Thereby, a comparative composition for removing material from amicroelectronic device comprising tungsten wiring (D′-4) was obtained.The pH of the obtained cleaning agent was 4.5.

The first compositions (D-1) to (D-5) and the comparative compositions(D′-1) to (D′-4) were tested for anticorrosiveness to tungsten, anability to remove metallic residues, and an ability to remove abrasivegrains and evaluated. Table 1 summarizes the results.

TABLE 1 Composition of cleaning agent Quaternary Performance of cleaningagent Organic ammonium Chelating Other Water Anticorro- Ability toAbility to amine (A) hydroxide (B) agent (C) component (W) sivenessremove remove Content Content com- Content Content Content to metallicabrasive component (%) component (%) ponent (%) component (%) (%) pHtungsten residues grains (D-1) TEP 0.14 TMAH 0.06 EDTA 0.002 — 99.8013.2 ∘ ∘ ∘ (D-2) MEA 0.14 TMAH 0.05 EDTA 0.004 — 99.81 12.5 ∘ ∘ ∘ (D-3)TEP 0.14 TMAH 0.06 EDTA 0.002 — 99.80 12.4 ∘ ∘ ∘ (D-4) TEP 0.14 TMAH0.06 HEDTA 0.004 99.80 12.9 ∘ ∘ ∘ (D-5) TEP 0.07 TMAH 0.02 HEDTA 0.00699.90 9.2 ∘ ∘ ∘ (D′-1) TMAH 0.06 EDTA 0.002 99.94 10.4 ∘ x □ (D′-2) TEP0.14 EDTA 0.002 99.86 9.1 ∘ ∘ x (D′-3) TEP 0.14 TMAH 0.06 99.80 13.4 ∘ x∘ (D′-4) EDTA 0.100 Oxalic acid 5.00 94.90 4.5 □ ∘ x

Evaluation of Anticorrosiveness to Tungsten

Evaluation of anticorrosiveness to tungsten was performed by immersing awafer having a tungsten single layer film in the cleaning agents ofExamples 1 to 5 and Comparative Examples 1 to 4, and determining aconcentration of tungsten eluted from the wafer in the composition. Itwas determined that anticorrosiveness of the first composition totungsten was better as the amount of tungsten eluted per unit area wassmaller.

The procedure of the evaluation method was:

(1) Pretreatment of Wafer Having Tungsten Single Layer Film

A wafer having a tungsten single layer film (made by Advanced MaterialsTechnology Inc., obtained by vapor-depositing a tungsten metal at athickness of 2 μm on a silicon substrate) was cut into a piece 1.0 cmlong by 2.0 cm wide, immersed in a 10% acetic acid aqueous solution for1 minute, and washed with water.

(2) Elution of Tungsten

In 10 g of each of the first and comparative compositions, thepretreated piece of the wafer having a tungsten single layer film wasimmersed for 3 minutes at 25° C. before removal from the composition.

(3) Measurement of Amount of Tungsten Eluted

5 g of the first composition subsequent to elution was collected, andthe pH thereof was adjusted to 3.0 with a nitric acid aqueous solution.Then, water was added until the total amount reached 10 g, and ameasuring liquid was prepared. The concentration of tungsten in themeasuring liquid was measured using an ICP-MS analysis apparatus(inductively coupled plasma source mass spectrometer) (made by AgilentTechnologies, Inc., Agilent 7500cs type).

(4) Evaluation and Determination of Anticorrosiveness to Tungsten

The concentration of tungsten was substituted into the followingequation (1), and the amount of tungsten eluted (ng/cm²) was calculated:

$\begin{matrix}{{{Equation}\mspace{14mu} 1}\mspace{635mu}} & \; \\{{{Amount}\mspace{14mu} {of}\mspace{14mu} {tungsten}\mspace{14mu} {eluted}\mspace{14mu} ( {{ng}\text{/}{cm}^{2}} )} = \frac{W_{con} \times F\; 1 \times F\; 3}{F\; 2 \times S_{W}}} & (1)\end{matrix}$

wherein, W_(con)=tungsten concentration in the measuring liquiddetermined by the ICP-MS analysis (ppb (ng/g)); F1=amount of the firstcomposition in which the test piece is immersed (g); F2=amount of thefirst composition collected before adjusting the pH (g); F3=amount ofthe measuring liquid (g); and S_(w)=area of a tungsten single layer filmin the wafer having a tungsten single layer film (cm²).

Anticorrosiveness to tungsten was determined from the calculated amountof tungsten eluted according to the following criteria:

∘: Less than 15 ng/cm²□: 15 ng/cm² to 20 ng/cm²x: Not less than 20 ng/cm²

Method for Evaluating Ability to Remove Metallic Residues

Evaluation of an ability to remove metallic residues was performed asfollows: a wafer having a silicon oxide single layer film was immersedin an aqueous solution containing zinc, iron, and magnesium metal ionsto contaminate the wafer; the wafer was then immersed in the cleaningagents of Examples 1 to 5 and Comparative Examples 1 to 4; and theconcentrations of zinc, iron, and magnesium metal ions eluted from thesurface of the wafer in the cleaning agents of Examples 1 to 5 andComparative Examples 1 to 4 were determined with an ICP-MS analysisapparatus.

It was determined that an ability to remove metallic residues was higheras the amount of metal ions eluted per wafer unit area was larger.

The procedure of the evaluation method was:

(1) Pretreatment of Wafer Having a Silicon Oxide Single Layer Film

A silicon wafer having a silicon oxide single layer film (made byADVANTEC Co., Ltd., “P-TEOS 1.5μ,” thickness of silicon oxide=1.5 μm.)was cut into a piece 1.0 cm long by 2.0 cm wide, immersed in a 10%acetic acid aqueous solution for 1 minute, and washed with water.

(2) Preparation of Aqueous Solution Containing Metal Ions

Water was added to 0.1 parts of zinc nitrate, 0.1 parts of iron nitrate,and 0.1 parts of magnesium nitrate so that the total amount was 100 g,to prepare an aqueous solution containing 0.1% metal ions of zinc, 0.1%metal ions of iron, and 0.1% metal ions of magnesium.

(3) Contamination Treatment of Wafer with Metal Ion Aqueous Solution

The pretreated piece of the wafer having a silicon oxide single layerfilm was immersed in 10 g of the aqueous solution containing the metalions for 1 minute, and then dried by nitrogen blow. Thereby, the metalions were attached to the surface of the wafer.

(4) Washing of Wafer

In 10 g of each of the first and comparative compositions, the piece ofthe wafer having a silicon oxide single layer film that was subjected tothe contamination treatment was immersed for 3 minutes at 25° C.,followed by removing the wafer from the composition.

(5) Measurement of Concentration of Metal Ions Eluted in Cleaning Agentfrom Surface of Wafer

5 g of the second composition after the wafer was immersed wascollected, and the pH thereof was adjusted to 3.0 with a nitric acidaqueous solution. Then, water was added until the total amount reached10 g, and a measuring liquid was prepared. The concentrations of metalions of zinc, of iron, and of magnesium contained in the measuringliquid were measured using an ICP-MS analysis apparatus.

(6) Evaluation and Determination of Ability to Remove Metallic Residues

An amount of each metal ion eluted was calculated using the followingequation:

$\begin{matrix}{{{Equation}\mspace{14mu} 2}\mspace{635mu}} & \; \\{{{Amount}\mspace{14mu} {of}\mspace{14mu} {metal}\mspace{14mu} {ions}\mspace{14mu} {eluted}\mspace{14mu} ( {{ng}\text{/}{cm}^{2}} )} = \frac{{Metal}_{con} \times G\; 1 \times G\; 3}{G\; 2 \times S_{{SiO}\; 2}}} & (2)\end{matrix}$

wherein, Metal_(con)=ion concentration of each metal in the measuringliquid determined by ICP-MS analysis (ppb(ng/g)); G1=amount of thefirst/second composition in which a test piece is immersed (g);G2=amount of the first/second composition collected before adjusting thepH (g); G3=amount of the measuring liquid (g); and S_(SiO2)=area of thesilicon oxide film in the wafer having a single layer film of siliconoxide (cm²)

From the total amount of the calculated amounts of the ions ofrespective metals eluted, an ability to remove metallic residues wasdetermined according to the following criteria:

∘: Not less than 15 ng/cm²□: 10 ng/cm² to 15 ng/cm²x: Less than 10 ng/cm²

Method for Measuring Ability to Remove Abrasive Grains

Evaluation of an ability to remove abrasive grains was performed. Awafer having a silicon nitride single layer film was immersed in a CMPslurry used at a CMP step for a tungsten wiring to be contaminated.Then, the wafer was immersed in the cleaning agent of Examples 1 to 5and Comparative Examples 1 to 4 for a semiconductor provided with atungsten alloy wiring. After the wafer after washing was dried, a degreeof remaining abrasive grains per visual field was observed using an SEM(scanning electron microscope). It was determined that an ability toremove abrasive grains was higher as the number of the remainingabrasive grains per visual field was smaller.

The procedure of the evaluation method was:

(1) Washing of Wafer Having Silicon Nitride Single Layer Film

A wafer having a silicon nitride single layer film (made by AdvancedMaterials Technology Inc., “PE-CVDSiN 1.5μ,” thickness of siliconnitride=1.0 μm.) was immersed in a 10% acetic acid aqueous solution for1 minute, and then washed with water.

(2) Contamination Treatment with CMP Slurry

The wafer having a silicon nitride single layer film was immersed in aCMP slurry (made by Cabot Corporation, W7000, principal component ofabrasive grains of SiO₂, average particle size of 0.2 μm) for 1 minute,and then dried by nitrogen blow. The obtained wafer after thecontamination treatment was cut into 1.0 cm long by 1.5 cm wide.

(3) Washing with Cleaning Agent for Semiconductor Provided with TungstenWiring

In 10 g of each of the first and comparative compositions, a waferhaving a contaminated silicon nitride single layer film was immersed,and left to stand for 3 minutes at 25° C. Then, the wafer having asilicon nitride single layer film was removed from the firstcomposition, and dried by nitrogen blow.

(4) SEM Observation of Surface of Wafer Having Silicon Nitride SingleLayer Film after Washing

The surface of the wafer having a silicon nitride single layer filmafter washing was observed at a magnification of 10,000 using an SEM(made by Hitachi High-Technologies Corporation, model name S-4800).

(5) Evaluation of Ability to Remove Abrasive Grains

From an SEM image of the surface of the wafer, the number of remainingabrasive grains per visual field was checked, and an ability to removeabrasive grains was determined by the following criteria:

∘: Less than 10□: 10 to 20x: Not less than 20

As shown in Table 1, the first composition according to Examples 1 to 5had favorable results in all three evaluated items. On the other hand,in Comparative Example 1 containing no organic amine (A), an ability toremove metallic residues was poor, and an ability to remove abrasivegrains was also insufficient. In Comparative Example 2 containing noquaternary ammonium hydroxide (B), an ability to remove abrasive grainswas poor. In Comparative Example 3 containing no chelating agent (C), anability to remove metallic residues was poor. Furthermore, inComparative Example 4 containing only the chelating agent (C) and theoxalic acid, anticorrosiveness to tungsten was insufficient, and anability to remove abrasive grains was poor.

Hereinafter, preparation of cleaning agents for a semiconductor providedwith a copper wiring according to Examples 6 to 11 and ComparativeExamples 5 to 12 will be described.

Example 6

0.07 parts of N-aminoethylpiperazine (AEP) (purity of 99%, made by WakoPure Chemical Industries, Ltd.) and 0.05 parts of gallic acid (tradename: gallic acid monohydrate, purity of 99%, made by Wako Pure ChemicalIndustries, Ltd.) were added to a 300-ml container made of polyethylene.Next, 0.28 parts of a 25% TMAH aqueous solution (C-1) (trade name: 25%TMAH, an aqueous solution with purity of 25%, made by Tama ChemicalsCo., Ltd.), and 0.18 parts of L-ascorbic acid (trade name: L(+)-ascorbicacid (L-AA), purity of 99.5%, made by Nacalai Tesque, Inc.) were added.Then, 99.4 parts of water was added so that the total weight might be100 parts. The solution was stirred by a magnetic stirrer to obtain asecond composition for removing material from a microelectronic devicecomprising copper wiring (F-6) was obtained.

Example 7

The same operation as that in Example 6 was performed except that 0.10parts of N-isobutylpiperazine (purity of 98%, made by Wako Pure ChemicalIndustries, Ltd.) was used instead of AEP in Example 6, a blendingamount of TMAH was changed to 0.40 parts, and water was added so thatthe total weight might be 100 parts. Thereby, a second composition forremoving material from a microelectronic device comprising copper wiring(F-7) was obtained.

Example 8

The same operation as that in Example 6 was performed except that 0.13parts of N-hydroxypropyl piperazine (purity of 98% made by Wako PureChemical Industries, Ltd.) was used instead of AEP in Example 6, ablending amount of TMAH was changed to 0.52 parts, and water was addedso that the total weight might be 100 parts. Thereby, a secondcomposition for removing material from a microelectronic devicecomprising copper wiring (F-8) was obtained.

Example 9

The same operation as that in Example 6 was performed except that 0.08parts of 1,4-dimethylpiperazine (purity of 98%, made by Koei ChemicalCo., Ltd.) was used instead of AEP in Example 6, 0.32 parts of a 25%TEAH aqueous solution (C-2) (an aqueous solution with purity of 25%,made by Wako Pure Chemical Industries, Ltd.) was used instead of TMAH,0.18 parts of D-ascorbic acid (D-AA) (trade name: D(+)-ascorbic acid,purity of 99.5%, made by Nacalai Tesque, Inc.) was used instead ofL(+)-ascorbic acid, and water was added so that the total weight mightbe 100 parts. Thereby, a second composition for removing material from amicroelectronic device comprising copper wiring (F-9) was obtained.

Example 10

The same operation as that in Example 9 was performed except that 0.08parts of 1,4-(bisaminopropyl)piperazine (purity of 98%, made by KoeiChemical Co., Ltd.) was used instead of 1,4-dimethylpiperazine inExample 9, 0.52 parts of a 25% TMAH aqueous solution was used instead ofTEAH, and water was added so that the total weight might be 100 parts.Thereby, a second composition for removing material from amicroelectronic device comprising copper wiring (F-10) was obtained.

Example 11

The same operation as that in Example 10 was performed except that 0.08parts of N-aminoethylmorpholine (purity of 98%, made by Koei ChemicalCo., Ltd.) was used instead of 1,4-(bisaminopropyl)piperazine in Example10, the blending amount of TMAH was changed to 0.32 parts, and water wasadded so that the total weight might be 100 parts. Thereby, a secondcomposition for removing material from a microelectronic devicecomprising copper wiring (F-11) was obtained.

The content of each component is shown in Table 2 in % by weight aboutthe cleaning agents for a semiconductor provided with a copper wiring(F-6) to (F-11) according to Examples 6 to 11.

The content of the quaternary ammonium hydroxide (Q) is shown in % byweight by converting the blended quaternary ammonium hydroxide aqueoussolution into a solid content. In the used cyclic polyamine (P), bondinggroups at the R¹ to R³ positions in the above general formula (1) andgeneral formula (2) are shown in Table 3.

TABLE 2 Polyphenol based reducing agent Quaternary having 2 to ammoniumCyclic polyamine 5 hydroxyl groups hydroxide Ascorbic acid WaterCleaning Content Name of Content Name of Content Name of Content Contentagent Name of component (%) component (%) component (%) component (%)(%) (F-6) N-Aminoethylpiperazine 0.07 Gallic acid 0.05 TMAH 0.07 L-AA0.18 99.6 (F-7) N-isobutylpiperazine 0.10 Gallic acid 0.05 TMAH 0.10L-AA 0.18 99.6 (F-8) N- 0.13 Gallic acid 0.05 TMAH 0.13 L-AA 0.18 99.5hydroxypropylpiperazine (F-9) 1,4-dimethylpiperazine 0.08 Gallic acid0.05 TEAH 0.08 D-AA 0.18 99.6 (F-10) 1,4- 0.08 Gallic acid 0.05 TMAH0.13 D-AA 0.18 99.6 (bisaminopropyl)piperazine (F-11)N-aminoethylmorpholine 0.08 Gallic acid 0.05 TMAH 0.08 D-AA 0.18 99.6

TABLE 3 Cyclic polyamine component component component Name of componentat R¹ at R² at R³ N-Aminoethylpiperazine H CH₂CH₂NH₂N-isobutylpiperazine H CH₂CH(CH₃)₂ N-hydroxypropylpiperazine HCH₂(CH₂)₂OH 1,4-dimethylpiperazine CH₃ CH₃1,4-(bisaminopropyl)piperazine CH₂(CH₂)₂NH₂ CH₂(CH₂)₂NH₂N-aminoethylmorpholine CH₂CH₂NH₂

Comparative Example 5

The same operation as that in Example 6 was performed except that thegallic acid in Example 6 was not added. Thereby, a comparisoncomposition for a semiconductor provided with a copper wiring (F′-5) wasobtained.

Comparative Example 6

The same operation as that in Example 7 was performed except that theL-ascorbic acid in Example 7 was not added. Thereby, a comparisoncomposition for a semiconductor provided with a copper wiring (F′-6) wasobtained.

Comparative Example 7

The same operation as that in Example 8 was performed except that 0.13parts of piperazine (purity of 98%, made by Koei Chemical Co., Ltd.) wasadded instead of AEP in Example 8. Thereby, a comparison composition fora semiconductor provided with a copper wiring (F′-7) was obtained.

Comparative Example 8

The same operation as that in Example 11 was performed except that 0.08parts of N-methylmorpholine (purity of 98%, made by Koei Chemical Co.,Ltd.) was used instead of N-aminoethylmorpholine in Example 11. Thereby,a comparison composition for a semiconductor provided with a copperwiring (F′-8) was obtained.

Comparative Example 9

The same operation as that in Example 8 was performed except that 0.08parts of 4-picoline (purity of 97%, made by Koei Chemical Co., Ltd.) wasused instead of N-hydroxypropyl piperazine in Example 8. Thereby, acomparison composition for a semiconductor provided with a copper wiring(F′-9) was obtained.

Comparative Example 10

The same operation as that in Example 8 was performed except that 0.08parts of triethanolamine (purity of 98%, made by Wako Pure ChemicalIndustries, Ltd.) was used instead of N-hydroxypropyl piperazine inExample 8. Thereby, a comparison composition for a semiconductorprovided with a copper wiring (F′-10) was obtained.

Comparative Example 11

The same operation as that in Example 6 was performed except that 0.08parts of tetraethylenepentamine (trade name: AFR-AN6, purity of 99.2%,made by Tosoh Corporation) was used instead of AEP in Example 6.Thereby, a comparison composition for a semiconductor provided with acopper wiring (F′-11) was obtained.

Comparative Example 12

The same operation as that in Example 6 was performed except that 0.20parts of citric acid (purity of 99%, made by Nacalai Tesque, Inc.) wasadded while the gallic acid and L-ascorbic acid were removed. Thereby, acomparison composition for a semiconductor provided with a copper wiring(F′-12) was obtained.

The content of each component is shown in Table 4 in % by weight forcomparative compositions (F′-5) to (F′-12) in Comparative Examples 5 to12. The content of the quaternary ammonium hydroxide is shown in % byweight by converting the blended quaternary ammonium hydroxide aqueoussolution into a solid content. In the used cyclic polyamine (P), bondinggroups at the R¹ to R³ positions in the above general formula (1) andgeneral formula (2) are shown in Table 5.

TABLE 4 Polyphenol based reducing agent Quaternary having 2 to 5ammonium Clean- Cyclic polyamine hydroxyl groups hydroxide Ascorbic acidOther component water ing Content Name of Content Name of Content Nameof Content Name of Content Content agent Name of component (%) component(%) component (%) component (%) component (%) (%) (F′-5)N-aminoethylpiperazine 0.07 — — TMAH 0.07 L-AA 0.18 — 0.00 99.7 (F′-6)N-isobutylpiperazine 0.10 Gallic acid 0.05 TMAH 0.10 — — — 0.00 99.7(F′-7) Piperazine 0.13 Gallic acid 0.05 TMAH 0.13 L-AA 0.18 — 0.00 99.5(F′-8) N-methylmorpholine 0.08 Gallic acid 0.05 TEAH 0.08 D-AA 0.18 —0.00 99.6 (F′-9) 4-picoline 0.08 Gallic acid 0.05 TMAH 0.13 L-AA 0.18 —0.00 99.6 (F′-10) Triethanolamine 0.08 Gallic acid 0.05 TMAH 0.13 L-AA0.18 — 0.00 99.6 (F′-11) Tetraethylenepentamine 0.07 Gallic acid 0.05TMAH 0.07 L-AA 0.18 — 0.00 99.6 (F′-12) N-aminoethylpiperazine 0.07 — —TMAH 0.07 — — Citric acid 0.20 99.7

TABLE 5 Cyclic polyamine Composition Composition Composition Name ofcomponent at R¹ at R² at R³ N-aminoethylpiperazine H CH₂CH₂NH₂N-isobutylpiperazine H CH₂CH(CH₃)₂ Piperazine H H N-methylmorpholine CH₃4-picoline Triethanolamine Tetraethylenepentamine N-aminoethylpiperazineH CH₂CH₂NH₂

In the second compositions (F-6) to (F-11) prepared in Examples 6 to 11and the comparative compositions (F′-5) to (F′-12) prepared inComparative Examples 5 to 12, an ability to remove organic residues, anability to remove abrasive grains, an ability to remove metallicresidues, and anticorrosiveness to the copper wiring were measured andevaluated using the following methods. Table 6 shows the evaluationresult.

TABLE 6 Ability Ability Ability Anticor- to remove to remove to removerosiveness Cleaning organic abrasive metallic to copper agent residuesgrains residues wiring Example 6 (F-6) ∘ ∘ ∘ ∘ Example 7 (F-7) ∘ ∘ ∘ ∘Example 8 (F-8) ∘ ∘ ∘ ∘ Example 9 (F-9) ∘ ∘ ∘ ∘ Example 10  (F-10) ∘ ∘ ∘∘ Example 11  (F-11) ∘ ∘ ∘ ∘ Comparative (F-5) ∘ ∘ ∘ x Example 5Comparative (F′-6)  ∘ ∘ x x Example 6 Comparative (F′-7)  x x ∘ ∘Example 7 Comparative (F′-8)  x x ∘ ∘ Example 8 Comparative (F′-9)  x x∘ ∘ Example 9 Comparative  (F′-10) x x ∘ ∘ Example 10 Comparative (F′-11) ∘ ∘ ∘ x Example 11 Comparative  (F′-12) ∘ ∘ ∘ x Example 12

Method for Evaluating Ability to Remove Organic Residues

Evaluation of an ability to remove organic residues using the cleaningagents of Examples 6 to 11 and Comparative Examples 5 to 12 was madeaccording to the following procedure:

(1) Washing of Copper-Plated Silicon Wafer

A wafer obtained by performing copper plating on a silicon wafer (madeby Advanced Materials Technology Inc., “Cu plated 10000A Wafer,”thickness of copper plating=1.0 μm) was cut into a piece 1.5 cm long by1.5 cm wide. The cut wafer was immersed for 1 minute in a 10% aceticacid aqueous solution, and washed with water.

(2) Preparation of Organic Residue Liquid

0.4 g of benzotriazole, 0.6 g of a hydrogen peroxide solution at aconcentration of 30%, and 200 g of water were mixed, and adjusted withchloride so that the pH was about 3.0, thus preparing an organic residueliquid.

(3) Production of Copper Plated Wafer to which Organic Residues Adhere

The copper plated wafer was immersed in the organic residue liquidprepared in (2) for 60 seconds. Then, the wafer was immersed in waterfor 60 seconds to produce a copper plated wafer to which organicresidues adhered.

(4) Check of Amount of Organic Residues Adhering to Copper Plated Wafer

The amount of organic residues adhering to the copper plated wafer waschecked by measuring an amount of nitrogen derived from benzotriazole,which was an organic residue product, using an X ray photoelectronspectroscopy (XPS) apparatus (made by ULVAC-PHI, Inc., ESCA-5400 type).

Specifically, using XPS, the number of photoelectrons was measured at abinding energy from 397 eV to 399 eV, and a peak area value at a bindingenergy from 397.5 to 398.4 eV derived from nitrogen was determined. MgKαrays (1253.6 eV) were used as a soft X ray.

(5) Removal of Organic Residue Adhering to Copper Plated Wafer

In 50 g of each of the second compositions, the copper plated waferproduced in (3) to which organic residues adhered was immersed for 3minutes to remove the organic residues from the copper plated wafer.Then, the copper plated wafer was immersed in 1 L of water for 60seconds, and the wafer surface was dried by a nitrogen stream.

(6) Check of Amount of Organic Residues that Remained in Copper PlatedWafer

Similarly to the case of (4), the amount of the organic residues thatremained on the copper plated wafer was checked by measuring an amountof nitrogen derived from benzotriazole, which was an organic residueproduct, using XPS.

(7) Evaluation and Determination of Ability to Remove Organic Residues

Two peak area values measured in (4) and (6) were substituted into thefollowing equation (3), and an organic residue removal rate wascalculated:

$\begin{matrix}{{{Equation}\mspace{14mu} 3}\mspace{655mu}} & \; \\{{{Organic}\mspace{20mu} {residue}\mspace{14mu} {removal}\mspace{14mu} {rate}\mspace{14mu} (\%)} = {\frac{( {{Xa} - {Xb}} )}{Xa} \times 100}} & \;\end{matrix}$

wherein, Xa=Peak area value of nitrogen derived from benzotriazolebefore organic residues are removed; Xb=Peak area value of nitrogenderived from benzotriazole after organic residues are removed

An ability to remove organic residues was determined from the calculatedorganic residue removal rate according to the following criteria:

∘: Organic residue removal rate is not less than 90%.x: Organic residue removal rate is less than 90%.

Method for Evaluating Ability to Remove Abrasive Grains

Evaluation of an ability to remove abrasive grains using the cleaningagents of Examples 6 to 11 and Comparative Examples 5 to 12 was madeaccording to the following procedure:

(1) Washing of Copper Plated Silicon Wafer

A copper plated silicon wafer was washed by the same method as that usedin evaluation of an ability to remove organic residues.

(2) Contamination Treatment with CMP Slurry

The washed copper-plated silicon wafer was immersed in a CMP slurry(made by Cabot Corporation, W7000, principal component of the abrasivegrains of SiO₂, average particle size of 0.2 μm) for 1 minute, and driedby nitrogen blow. The wafer subjected to the contamination treatment wascut into a piece 1.0 cm long by 1.5 cm wide to obtain a sample forevaluation.

(3) Washing with the Second Composition

In 10 g of each of the second compositions, the sample for evaluationobtained in (2) was immersed, and left to stand for 3 minutes at 25° C.Then, the sample for evaluation was extracted from said composition, anddried in nitrogen blow.

(4) SEM Observation of Surface of Evaluation Sample after Washing

The surface of the washed evaluation sample obtained in (3) was observedat a magnification of 10,000 using an SEM (made by HitachiHigh-Technologies Corporation, model name S-4800).

(5) Evaluation and Determination of Ability to Remove Abrasive Grains

From the SEM image, it was determined that the ability to removeabrasive grains was higher as the number of residual abrasive grains pervisual field was smaller. Specifically, the number of residual abrasivegrains per visual field was checked, and determination was madeaccording to the following criteria:

∘: Less than 10□: 10 to 20x: Not less than 20

Method for Evaluating Ability to Remove Metallic Residues

Evaluation of an ability to remove metallic residues using the cleaningagents of Examples 6 to 11 and Comparative Examples 5 to 12 wasperformed according to the following procedure:

(1) Pretreatment of Wafer Having Silicon Oxide Single Layer Film

A silicon wafer having a silicon oxide single layer film (made byADVANTEC Co., Ltd., “P-TEOS 1.5μ”, thickness of silicon oxide=1.5 μm.)was cut into a piece 1.0 cm long by 2.0 cm wide, immersed in a 10%acetic acid aqueous solution for 1 minute, and washed with water.

(2) Preparation of Aqueous Solution Containing Metal Ions

Water was added to 0.1 parts of zinc nitrate, 0.1 parts of iron nitrate,and 0.1 parts of magnesium nitrate so that the total amount might be 100g, thereby to prepare an aqueous solution containing 0.1% metal ions ofzinc, 0.1% metal ions of iron, and 0.1% metal ions of magnesium.

(3) Contamination Treatment of Wafer with Metal Ion Aqueous Solution

The pretreated piece of the wafer having a silicon oxide single layerfilm was immersed in 10 g of the aqueous solution containing metal ionsfor 1 minute, and dried by nitrogen blow. Thereby, the metal ions wereattached to the surface of the wafer.

(4) Washing of Wafer

In 10 g of each of the second compositions, the piece of thecontaminated wafer having a silicon oxide single layer film wasimmersed. After the piece of the wafer was left to stand for 3 minutesat 25° C., the piece of the wafer was extracted from the compositions.

(5) Measurement of Concentration of Metal Ions in Second Compositionsfrom Surface of Wafer

5 g of the composition after the wafer was immersed was collected, andthe pH thereof was adjusted to 3.0 with a nitric acid solution. Then,water was added until the total amount reached 10 g, and a measuringliquid was prepared. The concentration of metal ions of zinc, that ofiron, and that of magnesium contained in the measuring liquid weremeasured using an ICP-MS analysis apparatus.

(6) Calculation of Amount of Metal Ions Eluted in Cleaning Agent fromSurface of Wafer

An amount of ions of each metal eluted was calculated using equation 2.

(7) Evaluation and Determination of Ability to Remove Metallic Residues

An ability to remove metallic residues was evaluated from the totalamount of the respective calculated amounts of metal ions eluted, and itwas determined that an ability to remove metallic residues was higher asthe amount of metal ions eluted per unit area of the wafer was larger.Specifically, an ability to remove metallic residues was determinedaccording to the following criteria:

∘: Not less than 15 ng/cm²□: 10 ng/cm² to 15 ng/cm²x: Less than 10 ng/cm²

Method for Evaluating Anticorrosiveness to Copper Wiring

Evaluation of anticorrosiveness to the copper wiring using the cleaningagents of Examples 6 to 11 and Comparative Examples 5 to 12 wasperformed according to the following procedure:

(1) Pretreatment of Wafer Having Copper Single Layer Film

A wafer having a copper single layer film (made by Advanced MaterialsTechnology Inc., a wafer obtained by vapor-depositing a copper metal ata thickness of 2 μm on a silicon substrate) was cut into a piece 1.0 cmlong by 2.0 cm wide, immersed in a 10% acetic acid aqueous solution for1 minute, and washed with water.

(2) Elution of Copper

In 10 g of each of the second compositions, the pretreated piece of thewafer having a copper single layer film was immersed. The piece was leftto stand for 3 minutes at 25° C., and removed from the cleaning agent.

(3) Measurement of Copper Ion Concentration

5 g of the second composition after the piece of the wafer having acopper single layer film was immersed was collected, and the pH thereofwas adjusted to 3.0 with a nitric acid aqueous solution. Then, water wasadded until the total amount reached 10 g, and a measuring liquid wasprepared. The copper ion concentration in the measuring liquid wasmeasured using an ICP-MS analysis apparatus.

(4) Calculation of Amount of Copper Ions Eluted

The concentration of copper ions was substituted into the followingequation (4), and the amount of copper ions eluted (ng/cm²) wascalculated:

$\begin{matrix}{{{Equation}\mspace{14mu} 4}\mspace{661mu}} & \; \\{{{Amount}\mspace{14mu} {of}\mspace{20mu} {copper}\mspace{14mu} {ions}\mspace{14mu} {eluted}\mspace{14mu} ( {µ\; {g/{cm}^{2}}} )} = \frac{{Cu}_{con} \times H\; 1 \times H\; 3}{H\; 2 \times S_{Cu}}} & \;\end{matrix}$

wherein, Cu_(con)=copper ion concentration in the measuring liquiddetermined by the ICP-MS analysis (ppb (ng/g)); H1=amount of the secondcomposition in which the test piece is immersed (g); H2=amount of thesecond composition collected before adjusting the pH (g); H3=amount ofthe measuring liquid (g); and S_(cu)=area of a copper single layer filmin the wafer having a copper single layer film (cm²)

(5) Evaluation and Determination of Anticorrosiveness to Copper Wiring

Anticorrosiveness to the copper wiring was evaluated from the calculatedamount of copper ions eluted. It was determined that anticorrosivenessto the copper wiring was better as the amount of copper ions eluted perunit area of the wafer having a copper single layer film was smaller.Specifically, anticorrosiveness to the copper wiring was determinedaccording to the following criteria:

∘: Less than 15 ng/cm²□: 15 ng/cm² to 20 ng/cm²x: Not less than 10 ng/cm²

As shown in Table 6, the second compositions in Examples 6 to 11 hadfavorable results in all four evaluated items. On the other hand, inComparative Example 5 containing no polyphenol based reducing agenthaving 2 to 5 hydroxyl groups, anticorrosiveness to the copper wiringwas poor. In Comparative Example 6 containing no ascorbic acid, anability to remove metallic residues was poor and anticorrosiveness tothe copper wiring was poor. In Comparative Example 7 containing a cyclicpolyamine not included in the cyclic polyamine according to the presentinvention, Comparative Examples 8 and 9 containing a cyclic monoamineinstead of the cyclic polyamine, and Comparative Example 10 containing achain monoamine, an ability to remove organic residues and an ability toremove abrasive grains were all poor. Moreover, in Comparative Example11 containing a chain polyamine instead of the cyclic polyamine, andComparative Example 12 containing citric acid instead of the ascorbicacid, anticorrosiveness to the copper wiring was poor.

INDUSTRIAL APPLICABILITY

The compositions for removing material from a microelectronic devicecomprising metal wiring has an excellent ability to remove abrasivegrains derived from a polishing agent and an excellent ability to removemetallic residues on an insulating film, and has excellentanticorrosiveness to the metal wiring. Accordingly, the compositions canbe suitably used as a cleaning agent in a post-CMP step in themanufacturing process of the semiconductor in which a metal wiring isformed. Although the invention has been variously disclosed herein withreference to illustrative embodiments and features, it will beappreciated that the embodiments and features described hereinabove arenot intended to limit the invention, and that other variations,modifications and other embodiments will suggest themselves to those ofordinary skill in the art, based on the disclosure herein. The inventiontherefore is to be broadly construed, as encompassing all suchvariations, modifications and alternative embodiments within the spiritand scope of the claims hereafter set forth.

1. A composition comprising a cyclic polyamine, a polyphenol basedreducing agent (R) having 2 to 5 hydroxyl groups, a quaternary ammoniumhydroxide (Q), ascorbic acid (AA), and water, wherein said compositionis useful for the removal of material from a surface of amicroelectronic device, wherein said microelectronic device comprisescopper or copper alloy wiring, and wherein said cyclic polyamine isrepresented by the general formula (4) and/or formula (5):

wherein, R¹ represents a hydrogen atom, an alkyl group, an amino alkylgroup, or a hydroxyalkyl group; and R² represents an alkyl group, anamino alkyl group, or a hydroxyalkyl group,

wherein, R³ represents an amino alkyl group.
 2. The composition of claim1, wherein the material comprises post-CMP residue and/or contaminants.3. The composition according to claim 1, wherein the polyphenol basedreducing agent (R) is gallic acid.
 4. The composition according to claim1, wherein the quaternary ammonium hydroxide (Q) is a quaternaryammonium hydroxide (Q1) represented by the following general formula (6)

wherein, R⁴ to R⁷ each independently represent an alkyl group having 1to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms. 5.The composition according to claim 4, wherein the quaternary ammoniumhydroxide (Q) comprises tetramethylammonium hydroxide.
 6. Thecomposition according to claim 1, wherein the cyclic polyamine isselected from the group consisting of N-methylpiperazine,N-ethylpiperazine, N-isobutylpiperazine, N-aminomethylpiperazine,N-aminoethylpiperazine, N-aminopropylpiperazine,N-hydroxymethylpiperazine, N-hydroxyethylpiperazine,N-hydroxypropylpiperazine, 1,4-dimethylpiperazine,1,4-diethylpiperazine, 1,4-diisopropylpiperazine, 1,4-dibutylpiperazine,1-aminomethyl-4-methylpiperazine, 1-hydroxymethyl-4-methylpiperazine,1-aminoethyl-4-ethylpiperazine, 1-hydroxyethyl-4-ethylpiperazine,1,4-(bis aminoethyl)piperazine, 1,4-(bishydroxyethyl)piperazine,1,4-(bisaminopropyl)piperazine, 1,4-(bishydroxypropyl)piperazine,1-aminoethyl-4-hydroxyethylpiperazine,1-aminopropyl-4-hydroxypropylpiperazine, N-aminoethylmorpholine,N-aminopropylmorpholine, N-aminoisobutylmorpholine, and combinationsthereof.
 7. The composition according to claim 1, further comprising atleast one corrosion inhibitor.
 8. The composition according to claim 7,wherein the corrosion inhibitor comprises at least one species selectedfrom the group consisting of N-ribosylpurine, adenosine, guanosine,2-aminopurine riboside, 2-methoxyadenosine, N-methyladenosine,N,N-dimethyladenosine, trimethylated adenosine, trimethylN-methyladenosine, C-4′-methyladenosine, 3-deoxyadenosine, adenine,methylated adenine, dimethylated adenine,N4,N4-dimethylpyrimidine-4,5,6-triamine, 4,5,6-triaminopyrimidine,allantoin, hydroxylated C—O—O—C dimers, C—C bridged dimers, ribose,methylated ribose, tetramethylated ribose, methylated hydrolyzeddiribose compounds; xylose, glucose, purine, guanine, hypoxanthine,xanthine, theobromine, caffeine, uric acid, isoguanine,triaminopyrimidine, and combinations thereof.
 9. A method of removingpost-CMP residue and/or contaminants from a microelectronic devicehaving said residue and contaminants thereon, said method comprisingcontacting the microelectronic device with a composition for sufficienttime to at least partially clean said residue and contaminants from themicroelectronic device, wherein the microelectronic device comprisescopper or copper alloy wiring, wherein said composition comprises acyclic polyamine, a polyphenol based reducing agent (R) having 2 to 5hydroxyl groups, a quaternary ammonium hydroxide (Q), ascorbic acid(AA), and water, wherein said cyclic polyamine is represented by thegeneral formula (4) and/or formula (5):

wherein, R¹ represents a hydrogen atom, an alkyl group, an amino alkylgroup, or a hydroxyalkyl group; and R² represents an alkyl group, anamino alkyl group, or a hydroxyalkyl group,

wherein, R³ represents an amino alkyl group.
 10. A compositioncomprising an organic amine (A), a quaternary ammonium hydroxide (B), achelating agent (C), and water (W), having pH in the range of about 7.0to about 14.0, wherein said composition is useful for the removal ofmaterial from a surface of a microelectronic device, wherein saidmicroelectronic device comprises tungsten or tungsten alloy wiring. 11.The composition of claim 10, wherein the material comprises post-CMPresidue and/or contaminants.
 12. The composition according to claim 10claim 10, wherein the organic amine (A) is an alkanolamine (A1)represented by a following general formula (1) and/or a chain polyamine(A2) represented by a following general formula (2).

wherein, R¹ to R³ each independently represent a hydrogen atom or analkyl group that may be partially substituted by a hydroxyl group; andat least one of R¹ to R³ represents an alkyl group substituted by ahydroxyl group,

wherein, R⁴ to R⁸ each independently represent a hydrogen atom or analkyl group that may be partially substituted by a hydroxyl group; Y¹and Y² each independently represent an alkylene group; and n represents0 or an integer of 1 to
 4. 13. The composition according to claim 12,wherein the organic amine (A2) comprises tetraethylenepentamine.
 14. Thecomposition of claim 10, wherein the quaternary ammonium hydroxide (B)is a quaternary ammonium hydroxide (B1) represented by a followinggeneral formula (3).

wherein, R⁹ to R¹² each independently represent an alkyl group having 1to 3 carbon atoms and that may be partially substituted by a hydroxylgroup.
 15. The composition according to claim 14, wherein the quaternaryammonium hydroxide (B) comprises tetramethylammonium hydroxide.
 16. Thecomposition according to claim 10, wherein the chelating agent (C)comprises a species selected from the group consisting of phosphorusbased chelating agents (C1), amine based chelating agents (C2),aminocarboxylic acid based chelating agents (C3), carboxylic acid basedchelating agents (C4), ketone based chelating agents (C5), polymerchelating agents (C6), or any combination thereof.
 17. The compositionaccording to claim 16, wherein the chelating agent (C) comprisesethylenediamine tetraacetate.
 18. A method of removing post-CMP residueand/or contaminants from a microelectronic device having said residueand contaminants thereon, said method comprising contacting themicroelectronic device with the composition of claim 10 for sufficienttime to at least partially clean said residue and contaminants from themicroelectronic device, wherein the microelectronic device comprisestungsten or tungsten alloy wiring.
 19. (canceled)